Production of photographic sensitizing compounds



um compounds containing alkyl, thiol' ma, amino substituents. 1

Patented Apr. 11, 1939 Mart Bel-eat and John assign to EDM an Emmaiiritish company No Drawing. Application March 31, 1087, Borlnl No. reuse; n Great Blllllitlpi'll a. 1m 2 (01. sac-m) This invention relates to the production of I Photographic sensitizing compounds.

The most important known photographic sensitiaing compounds are the cyanine and carbocyanine dyestuiis which contain two heterocyclic nitrogen nuclei linked by, a' methine or polymethine chain, and it is a feature of all these compounds that the nitrogen atom in one nucleus is trivalent and the nitrogen atom in the other nucieusis quinque'valent. There are many known methods for producing cyanine and carbocyanine dyes, and in general these methods consist essentially in the condensation of quaternary salts of heterocyclic nitrogen compounds. One known method consists in the condensation of a quaternary salt of a heterocyclic nitrogen compound having a reactive methyl group in the a or 7 position to the nitrogen atom with a quaternary salt oi" a heterocyclic nitrogen compound containing a reactive thloether or selenoether grouping (including the reactive grouping of an alkyl salt oi a N-alkyl thione or selenone) or an aminoor substituted amino-vinyl groupingsuch as an acetanilido-vinyl grouping.

We have now found that compounds which may be considered'as the bases corresponding to the cysnine and carbocyanine 'dywtufis may be produced by adopting a processf'simiiar to the procas mentioned above for theproduction oi the dyestuffs, but substituting for the'aikyl salt 01' a h'eterocycl'ic nitrogen'compoundhaving a reactive methyl grouping in the a pr position to the nitrogen atom a quinoiine hase having a reactive methyl group in they or position ,to the nitrogen atom. Examples of suitable quincline bases are quinaldine; iepidine. naphthoquinaldina'naphthoiepidine and the correspondaikoxy. allwi- According to the present invention a'prooess tor the production of compounds which may be considered as the bases corresponding to the 1 cyanine and carbocyanine dyestiiiiscomprises condensing a quinoline' base having a reactive methyl group in the a or 1 position to the nitrogen with a quaternary salt of a heterocyclic nitrogencompound having a reactive thioether or seienoether grouping (including the reactive grouping of an alkyl salt or a N-alkyl thione or selenone) or an aminoor substituted aminovinyl grouping (including an arylamino-, acylamino-, or acylarylamino-vinyl grouping) a: or position to the nitrogen atom.

in the The reactions involving a thicether or selenoether grouping yield bases corresponding to the cyanine dyes whilst those involving the use of the amino-vinyl groupings yield bases cone spending to the carbocyaninedyes;

A symmetrical compound may be obtainedby condensing the quinbline 'hase containing the reactive methyl group, with a quaternary salt of a quinoline base having one-o1 the reactive groupings, such as thioether, selenoether and aminovinyl, indicated above; an unsymmetrical compoundmay be obtained by condensing the quinoline bases containing the reactive methyl group with'a quaternary salt of a diii'erent heterocyclic nitrogen compound.

The'heterocyclic nitrogen compounds whose albl salts may be condensed with the quinoline bases containing the reactive methyl groups in accordance with the present invention may be any 0! the compounds commonly used in'the preparation oi'lthe corresponding cyanine and carbocyanine dyestufls, for example, substituted and unsubstituted thiazoles, thiadolines, oxazoles,

oxazolines; selenazoles, seienazolines, Dyridines,-

v a I v I I iL-son oom-osn-sm ii The preparation of carbocyanine bases:-

'g +otmnn oomem of compounds may be produced in accordance with the, present invention corresponding to'tthe various types of cyanine and due settled out.

The manner in which the process of the pres ent invention may be carried out in practice is illustrated by the following specific examples which are given by way of example only:

Exurru: I

Preparation of z-mmmnwdmcmmzowudene quinaldme 3.8 grams of l-methylthiol-benzthiazole and 3.0 grams of methyl-p-toluene sulphonate were heated together for 2% hours at ISO- C. 3 grams 0! quinaldine and 20 cos. of pyridine were then added and the mixture was gently boiled under a reflux condenser ior halt an hour. The liquor was then poured into a large bulk of water when two layers formed. The aqueous layer was decanted from the oily layer, which was then stirred with spirit and ether. The solid which separated out was then filtered oil from the spirit and ether and washed and recrystallised from methyl alcohol, giving yellow prismatic needles, melting at 161-162 C.

Exsunll! l-methyldihudroqumclytidene- 2:2'-quina1diae 3.5 grams of 2-methylthiol-quinoline and 3.7 grams of methyl-p-toluene sulphonate were heated together for 3% hours at ISO-140 C. 2.85 grams of quinaldlne and 25 ccs. of pyridine were then added and the mixture was boiled gently under a reflux condenser for half an hour, after which it was poured into water when a resi- The aqueous layer was poured oil from the residue which was stirred up with spirit and filtered oil and washed The product was recrystallised from methyl alcohol to give orange prisms, melting at 153 C.

Enron: III

Preparation of Z-methuldihydrobenzthiaeolvlidone lepidinc 1.61 grams of l-methylthiol-benzthiazole, 1.86 grams oi methyl-p-toluene sulphonate were heated together for 3% hours at 130-140 C. 1.43 grams of lepidine and 20 cos. of pyridine were added and the mixture heated on a water bath for one hour, after which it was heated gently under a reflux condenser for twenty minutes. The mixture was then poured into water and the precipitate obtained recrystallised irom dilute methyl alcohol to yield orange red needles melting at 260 C.

ExulruIV Preparation 0/ Z-nrethubii-beazdihudrobenzthiazolylidenei1 -p-naphtho'quinaldine 4.6 grams of l-methylthiol-5:6-benzbenzthiapole and 3.! grams oi methyl-p-toluene sulphanate were heated together for live hours at C. 3.9 grams of p-naphthoquinaldine and 50 ccs. of pyridine were then added and the mixture heated under a reflux condenser for half an hour. The mixture was then added to water and the precipitate obtained filtered oil! and recrystal- Preparatton 0! lised from methyl alcohol and benzene. giving ochre coloured crystals melting at 305 C.

Preparation of Z-methul-dihydrobenzozazolulidene quinaldme 5 gramsoi i-methylthiol-benzoxazcle and 5.65 grams or methyl-p-toluene sulphonate were heated together for 3% hours at 130 C. 4.2

grams of quinoldine-and 25 cos. of pyridine were i then added and the mixture heated gently under a reflux condenser for twenty minutes. The mixture was then poured into water and the precipitate which formed separated out and recrystallised irom methyl alcohol to give orange yellow needles, melting at 244 C.

. m1. VI

1.3:3 trimethylindolylidene (2) ethulidene quinaldine 4.46 grams of 1:3:3-trimethyl-2-w-acetanllidovinyl-indoleninium iodide, 2.9 grams of quinaldine and 40 cos. of pyridine were heated gently under a reflux condenser (or half an hour, and the mixture was then poured into a mixture of ammonia and water. The aqueous liquor was decanted from the oily residue which was formed.

The oily residue was then dissolved in benzene, filtered oil and concentrated, and crystallised to yield brownish-yellow crystals which melted at 160 C.

Exsarnx VIII 4.46 grams 0! l.3.3-trimethyl-2-u-acetanilldovinylindolenium iodide and 3.74 grams of 6- ethoxyquinaldine were heated together for one hour at 160 C. The mixture obtained was allowed to cool and extracted with alcohol and the solution diluted with water. Ammonia was then added and the solution extracted with benzene. The benzene solution was washed with water and dried over sodium sulphate, concentrated and triturated with ammoniacal spirit. 0n standingi'or some time a solid separated out which" was recrystallized from spirit to yield brown yello needles melting at 192 C.

Exsurulx 4.46 grams oi 1.8.3-trimethyl-2-u-acetanilldovinylindolenium iodide and 3.14 grams of p-toluquinaidine were mixed together and heated at 180 C. and then maintained at a temperature 01160 C. for about 5a hour. The mixture obtained was then allowed to cool and extracted with warm alcohol. Ammonia was then added to the solution which was then extracted with benzene. The benzene solution was then washed with water and dried over sodium sulphate and afterwards concentrated. Ammoniacal spirit was then added to the concentrate and the solution allowed to stendwhen solid sehlreted out. This we: nltel ed on end reelstunned from spirit to yieldshinlnz yellow needles melting ot ll?! C.

. 3.62 grams -ol l-methylthiolhensthlesole and 3.72 grams of methyl-p-toluenesulphonete were heated tozether ammo-140' O. The mass was ellowed to cool end au ment flA-dlmethyll quinollneand woes; otpyrldlne wereedded :lhe mixture was first wormed one water both for about one hour 'e'nd then gently honed under s; l

' reflux condenser for about '20 minutes .on'd poured into A solid separated out and was 001- 4; leoted and washed. The solid was then extreoted llfi'oom-oi p ridine mesa sndthe whole was d ntly wormed for. ti hour on; wster hath and afterwards boiled gently under -a reflux condenser for nbmt hour and thenpoured into water. 'Astleky deposit was formedwhioh 1m diuolved lip-1 benzene hndoonoehfireted one allowed to stand yellow vsolid. meltin at 256 G. was deposited.

" Enters: peozselenaeeolvltdenequinaldl 141 mmafor"lj-metn itmol ts elm mox benzselenezole and 1.56 methyl-p tolueneslflphm 7 40 note were heateditoeether .s't-ldd" C. for "tour -;s.llowed to. cool and 1.2 w grams of .quineldlneend 25,005.; oi'ipypldlnewere -e.dded:-."lhe on water bath m1- ebout -hour 3nd then-Gently 3 under a 'l'eflus' condenser for ahohtifl andwas thenpoured into water and allowed to stand. A solideepora'ted out which was filtered oil dndi'eelfymllinedlmhybenaene ns orange meltihg'etMS' C; s

- of 'zoamvuls mn maioeede nvarobemmeolvumwnmm uene sulph'onate' were heated together It 1 40''.,

{or [our booth, The'mlxtulewesillowed to cool end Lida-pins of quineldine', list es; of p ndine were eddedeftet whieh-themixturewes gentlywarmed onewetet-hath to::-about% hou1 and; thenfzentlyboiled'under a for about. zllrminutes. h poured in o when a. solid out;

This was ebllectdl'lhd; extracted with Hot hen- 3 sene-and-diltei'ed'hot." ..On..oooling .theln'ltrete deposlted ox 'ange; mm min le at 235" P evention: a; z n flbenz't m llvl d fieouinaldtne iom hours. The mass theh ellowedto cool end'ZAiB grams of quinaldine end 25 oi.

llould."

2.25 grams or r-meth ltmolhs-meui lenedh br zmmlmwmwwu dine were added, The, mixture was may wormed on I. water bath for shout 55 hour end then gently boiled undone reflux condenser for a further mu'hmm after which It was poured v into water end ellowed to stand. A solid sepe voted out wlbsdllteoed-oi! and wished and'reory'stellised from hormone to yield Yellow needles, meltini at 226" C.- to ounce Men: 'm'

Prep orotion o1 s-mmmsmmdene d-sthwlthlogumaldine 5.4a rame. of l-methylthlolhenz thlizole and esa m. oi'methyl p-toluenesulphonotewere u hosted together Ift$t$$ hours at 14020. The x mixture was then ellowed toooolend 5 grams'jof 'd ethylthiolquinsldlne ind; 85 of pyridine were added The was first wen'ned'on e water bath for about 54 hourend theni'gently h'oiled under a reflux eondenser-dor otiout 20 minutes after whiohJt-xwe's littownttr' lendsllowed-to stand when-e. solldseperetedout. This was'illtered '01! end tram bellizene es y'e'llowneedls. shelf-ind st 185; C.

558 of methyHi-toluene-slflhhonete nm atogem rm emu nmueuao-uvc. 7

'Ihe;mixtuse-was1 then,e1lowed .to cool end 4* grams of d-methylthlol quinaldlne and Sided-oi 'hyridine' were edded. .The mixture was then I v gently war ed on a water bath to: about hi1! e hour' me. uterwm may nder e, reflux oondenses for twenty minutes.- 'end 'iinelly lfito water and .ellowe'd to stead. solid separated out, flIteiedoiL-washed end 4 ffomben'zene meltin ewe.

"fi d- 1: mad e-teamed 4.6 or" l gn'ethwlthlol di =i F eeolefmd 3.7, otmethyl p-toluenelshlphomte'were heated weather tor nvehours etiobout cool, 3.15 grams of p-tpluqulneldihe cos. .of pyrldi'ne The then gentliboiled undern-ietluxoondellser'lor. halt en -hour. after which it was 'poumdiinto.

.wstex ehd ellowed A 4 ..o -tm -Wne iorm' or glistening yellow lee flets'km'eltihg at 170-180 'C. The mixture then '01- -:ure v: a. s zefltly'boilei l \mdelgau reflux I or h ur hen pom-ed mmr w-- 4.3 om of iethmmoms-dlmethoxym benzthieeole-and 8,! grams of nzethgl-p-toluenv. Y sulphonete were; heated together st "C.' 1'or l and allowed to etoli LfA solid which was filtered-01f. and

ml its! our many: elo'ohol; Themsiduo s moment-momma! t y 4.6 grams of; l-methylthlol-id-henzhenzthi azoie and 3.7 grams oi methyl-p-toluenesulphwnate were heated tosetherior'iive hours at- 110-. 180 C. The mixture was then allowed to cool and 8.9 grams of fl-naphtho-quinaldine and 50 oi. 7 pyridine were added. This, mixture was then gently boiledunder aretiux condenser for about half'a'nl'hou j" and then poured into water. A solid separated out which was collected and and extracted with hot-methyl: alcohol. The residue was then-recrystallised roan-benzene to yield ochre coloured rhomhs and paralleleoipedsmeltinl at 305 C:

Exmu X 4.9 grams of i-ethylthiol-fitd-bensbensthiazole and) grams of ethyl-p-toluenesuiphooate were heated together at 150-189- 0. for 4% hours The mixture was then to cool and, grams 0! quinaldine and 30cc; 0! pyridine. were added. 'ihemixture was then gently boiled un do:- a reflux condenser for about half an hour, after which it was poured into water. A solid separated out, which was altered oil, washedand dissolved in hot acetic acid. 0n allowing to stand a.solid was deposited." This wasflltered oil. and the iiltratefwas rendered alkallne'with ammonia whens solid separated out. This was flitered on. washed and twice from spirit toyield yellow needles, melting at186 Cu CERTIFICATE OF oo REcTI on.

.Patent no. 2.15;,9 1.

mm: BARENT, 'ET 1L.

tered oil, extracted with hotmethy'l alcohol. residue recrystallised from bensene as orange-mambo melting at 326' C mmmm of z-mvmhuarmmum- 5.0 oi i-ethylthiolbenmthialole and 5.1 grams of ethe'l-r-toluenesulphonate were heated tot ether m1- fem-"hours at about rec-140' c. The inlxturewas then allowed to'cool and Ill gra ns oiquinaldine andlbecnotpyridinewere added. The mixture was then sently boiled under-ark iiux for aboutmu an hour. after which it poured into water and allowed to 5 stand; "rue-memo liquors'were decanted oil, and-the residue was triturated with spirit and filtered. The residue was then from methyl alcohol to yield yellow" prismatic needles, melting at are. 1

: V i l kprocess i'or the preparation of bases correspondin w l cyanine and ca -m ni c drestuiis heating in the presence of an 1 acid suhstanes a quinoline base contain igg a reactive rnethyrgroup in a. position of the group consisting are and 7 positions to the mmgen atom-. -wlth quaternaryaalhm' a heterocycl-ic nltroien compound selected irom the group-consisting oiaihyl quaternary salts,; havin; one "oi' the iollowing groups. aminovinyl acylalfiinovinyl, arylaminoviml and acylaryiaminovinyl groups substituted inthe a position to the nitrogen atom and alk'ylquaternary salts oi heterocyelic nitrogen containing a pyridine m; d more ne of followine srouos. aminovinyl, aoylaminovinyl, arylaminovlnyl and droupssubstituted in 1 positiontothenitrol'enatom.

' 23"Ih'e preparation of 1:8:3-trimeth1lindo- 4 lyiidene-(D-ethylidenequinaldme by 1:

8: 35trimethyl 2-r-indoleninium iodideyithouinaldine in'the presence oi anacld bindin:substanee.

Joanmvm mom April 11, 1939.

It is hereby certified that error appears in the printed specification of the chore nurnbered patent rec uiring correction as follows: Page 1, second column, line 16, for "thiadolinea" read thiezolines; line 56, at the bottom of the formu layfor "+c 11 m1cocn' m read +c 1 mcocn H and that the said Letters Patent should be read with this correction therein that the some may conform tothe record of the casein the Patent Office.

Signed and sealed this 13th day of June, A. p 1959;

' Henry ,Ven iirsd ale Acting Commissioner of Patents. 

